EP3109028B1 - Print head for co-extruding conformal battery separator and electrode - Google Patents
Print head for co-extruding conformal battery separator and electrode Download PDFInfo
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- EP3109028B1 EP3109028B1 EP16174205.1A EP16174205A EP3109028B1 EP 3109028 B1 EP3109028 B1 EP 3109028B1 EP 16174205 A EP16174205 A EP 16174205A EP 3109028 B1 EP3109028 B1 EP 3109028B1
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- Prior art keywords
- separator
- electrode
- nozzles
- print head
- merge
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0411—Methods of deposition of the material by extrusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
- B05C5/0254—Coating heads with slot-shaped outlet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
- B29C48/154—Coating solid articles, i.e. non-hollow articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/19—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their edges
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
- B29C48/307—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets specially adapted for bringing together components, e.g. melts within the die
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/49—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/695—Flow dividers, e.g. breaker plates
- B29C48/70—Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows
- B29C48/71—Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows for layer multiplication
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
- H01M50/406—Moulding; Embossing; Cutting
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3468—Batteries, accumulators or fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- This disclosure relates to fabricating batteries, more particularly fabricating batteries using a co-extrusion apparatus.
- a co-extrusion apparatus is one in which two or more materials are extruded simultaneously into a structure of some kind. This type of apparatus can be used in fabrication of batteries, simultaneously extruding electrodes with separators to form components of batteries.
- Examples of the co-extrusion approaches include US Patent Publication 20120156364 , in which interdigitated fingers of co-extruded materials are extruded from one print head type of apparatus. The materials are fed into feeding channels and combined as separate flows, then split and combined again until a structure of alternating stripes of the two materials is created as they exit the print head. In another approach, the side-by-side lateral structure extends to interdigitated stripes in the vertical direction as well. US Patent Publication 20140186519 teaches a means to generate this type of structure.
- US Patent Publication No. 20110217585 discusses batteries having integrated separators and methods of fabricating such batteries.
- the separators are formed in different ways, but generally formed directly on either the cathode or anode.
- the separators may be single layer or multi-layered. These approaches do not form the electrodes and separators simultaneously in an extrusion manner.
- Another approach uses electrophoretic deposition in sequential layers to form thin-film batteries.
- the sequential layers are formed using electrophoretic deposition.
- An example of this approach is shown in US Patent Publication 20130244102 .
- US 2013/0133201 A1 describes a method for generating a microchannel heat pipe on a substrate by co-extruding a primary material and a secondary material.
- US 2014/0186519 A1 describes a co-extrusion print head for multi-layer battery structures that is capable of extruding at least two layers vertically in a single pass.
- US2007/0108229 A1 describes extruding composite materials on a substrate by feeding a first material into a first channel and a second material into one or more second channels residing on at least one side of the first channel.
- a co-extrusion print head that has at least one separator inlet port, at least a first, second and third series of channels arranged to receive a separator material from the separator inlet port, at least one electrode inlet port, a fourth series of channels arranged to receive an electrode material from the electrode inlet port, a first merge portion connected to the first, second, third and fourth series of channels, the first merge portion positioned to receive and merge all the separator material into separator flow and the electrode material into an electrode flow, a second merge portion connected to the first merge portion, the second merge portion positioned to receive and merge the separator flows and the electrode flows, and an outlet port comprising a first set of nozzles and a second set of nozzles, where the outlet port is connected to the second merge portion, wherein the outlet port is configured to distribute the separator material into the first set of nozzles and the electrode material into the second set of nozzles, wherein the first set of nozzles are arranged to the top of and to the sides of
- FIG. 1 shows a prior art embodiment of a battery 10 with cathode 16, anode 12 and separator 14.
- the separator has a larger area than that of either electrode. The process cuts the separator into a larger size than the anode and cathode electrodes. When inserted into a full cell assembly, the larger separator prevents edge/side contact between the electrodes.
- FIG. 2 shows an example of a conventional battery manufacturing process for creating a full cell consisting of an anode, a cathode and a separator.
- the process manufactures the anode in one clean.
- the process produces an anode slurry formation at 21, then slot coats it onto a current collector at 23, with calendaring for thickness control at 25.
- the process then dries the anode at 27.
- the process forms a cathode slurry at 20, then slot coats it onto the current collector at 22 with calendaring for thickness control at 24.
- the cathode is dried at 26.
- Both electrodes undergo slitting at 29 and 28.
- Electrode slitting typically involves slitting a roll of electrode materials to a desired width.
- the final cell is then assembled at 31.
- the process 30 forms the anode, cathode and separator slurries at 32.
- the three slurries are then co-extruded using the print head disclosed here at 34 onto a current collector with calendaring for thickness control at 36.
- the combination of the structures are dried at 38.
- the remaining current collector is then assembled with the extruded structure at 40.
- Figures 4-7 show embodiments of battery structures manufacturable with the co-extrusion print head described here.
- the electrode 52 has a conformal separator that covers the top and sides of the electrode. Conformal, as that term is used here, means that the separator molds itself to the electrode.
- the electrode 42 may consist of a single material as in electrode 52. Alternatively, the electrode may consist of an interdigitated structure 56 shown in Figure 5 . The interdigitated structure may result from the co-extrusion print head as discussed in the previous patents mentioned above.
- the separator conforms to the electrodes, but in addition to only covering the top and sides of the electrode, it also extends onto the current collector. This provides additional separation between the anode and cathode.
- the separator 50 conforms to the electrode 52 with extensions such as 54.
- Figure 7 shows the similar structure, but the electrode consists of an interdigitated electrode 56.
- Figure 8 shows an embodiment of a print head 62.
- the print head 62 extrudes the structures as viscous slurries onto a target substrate 60.
- the materials may require drying or firing to remove the solvent and densify the structures.
- the inlet ports 64, 66 and 68 receive slurries that eventually exist the print head in a manner to form the electrode 52, or interdigitated electrode 56, and separator 50, with or without the extension 54.
- the print head of Figure 8 can form the structures of Figures 4-7 .
- Fluid paths and manifolds in the print head distribute separator and electrode slurries or inks.
- the electrode material 52 exits from one set of nozzles in the print head, as will be discussed in Figures 10-12 .
- the separator may consist of three different zones.
- the extension 54 may consist of one slurry, referred to here as S1.
- the sides 70 may consist of another slurry, referred to here as S2.
- the top layer 50 may consist of another slurry, S3.
- These slurries may all feed from the same slurry, forming a uniform layer over the electrode. Alternatively, the slurries may be different materials, to enable better isolation or enhance other characteristics of the batteries.
- the flows and feeds can be controlled as will be discussed in more detail later.
- Figure 10 shows a side view of one embodiment of a print head 62.
- the print head has a top plate 82 that seals the print head and a back fixture plate for aligning parts 72.
- the ink enters through the back plate 72 and feeds into the nozzles through manifolds 74, 76, and 80, depending upon the material.
- manifolds 74, 76, and 80 depending upon the material.
- the ink may move 'away' from the front of the page and flow into the output nozzles from the manifold 80.
- the stack of nozzle plates 78 form the extrusion nozzles through which the slurries ultimately exit the print head.
- Figure 11 shows a closer view of a portion 84 from the extrusion nozzles 78 from Figure 10 .
- the portion 86 is show in more detail in Figure 13 .
- the orientation of the print head is important to understand the configuration of the resulting structure.
- the substrate which may consist of the current collector, is on the 'top' of the print head and the materials exit the print head with the electrode material E exiting the nozzles such as 94 being on the substrate first, then covered by the separator slurry S3 from nozzle 96, with the separator slurry S2 from nozzles such as 92.
- the separator slurry S1 exits the print head at nozzles such as 90 and comes out onto the substrate in the same position as the electrode material. Walls such as 98 in the print head keep the materials isolated as they exit the interdigitation portion of the print head into a merge portion.
- Figure 13 shows the individual slurries separated from each other, the separator slurries and the electrode slurries are separated amongst themselves and from each other.
- the discussion of Figures 13-15 may be better understood with reference to Figure 12 .
- the print head 62 is shown in a block diagram.
- the print head has the inlet ports such as 64 for the separator slurry and 68 for the electrode slurry.
- the first portion of the print head has sections 83 and 81 for the electrode and separator slurries to be received.
- a first merge portion 85 then allows the separator slurries to merge into a separator flow and a separate portion 87 of the first merge portion to allow the electrodes to merge into an electrode flow.
- a second merge portion 89 then allows the separator flows and the electrode flows to merge together into one flow prior to exiting the print head at the output 91.
- Figures 14 and 15 are from the perspective of looking back from the outlet towards the nozzles from which the slurries flow.
- the slurries have traversed a first merge portion so the all of the separator 'S' slurries are merged together and all the 'E' slurries are merged together, but the 'S' slurries and 'E' slurries are still separate from each other.
- the 'S' slurries and 'E" slurries have merged. Note that this all occurs within the print head, and the resulting set of slurries exit the print head as merged flows, and the merged flows are in contact with each other but do not mix.
- FIGs 16-18 illustrate a method of operation in which a layer of separator material that is wider than the electrode material.
- the materials are being extruded in a direction either going into or out of the page.
- the separator material 50 is distributed into nozzles on top of and to the sides of the electrode material, forming a 'wider' stripe than the electrode material. This may be accomplished, in embodiments outside the scope of the present invention, without using the larger nozzles such as 92 shown in Figure 13 .
- the separator material 50 is 'higher' than the electrode material relative to the substrate 60. As the materials exit the print head, the separator material 50 begins to flow over electrode material 52 because it is no longer supported in the print head. Upon coming to rest on the substrate 60, the separator 50 settles over the electrode material and forms the extensions 54. The portion of the separator 50 that forms the extensions 54 will depend upon how many nozzles are used for the separator beyond the nozzles used for the electrode materials.
- Figures 19-22 show alternative embodiments of the battery structures having another layer on top of the top layer of separator S3. Typically, this layer will be a second top layer of separator, but may also consist of electrode material of the type opposite the first electrode.
- the electrode 52 has the separator 50 formed on top of it.
- the opposite electrode 100 is formed on top of the separator 50.
- Figure 20 shows the embodiment similar to Figure 19 , but with the interdigitated electrodes 56.
- Figures 21 and 22 show the embodiments with an anode added to the separator that has extensions 54 with and without the interdigitated electrodes.
- Figure 23 shows an alternative embodiment of a print head.
- the stack of plates 78 includes an extra set of extrusion nozzles.
- An exploded view of the portion 102 of the plates 78 is shown in Figure 24 .
- the channels 104 that dispense the separator S2 on the substrate next to the electrode material are larger than the previous S2 channels.
- the nozzles 96 through which the slurry S3 exits the print head now have another set of nozzles adjacent them, such as 106.
- the channels such as 106 dispense a fourth slurry S4 enables a multilayer composite separator.
- S3 and S4 consist of different separator materials. After drying, the S3 and S4 materials would have different materials, such a different porosity, insulating or thermal properties, etc.
- the additional slurry may be an electrode material that is of an opposite type of the first-used electrode material E. For example, if E is an anode material, S4 would be cathode material, or the opposite.
- co-extrusion print heads can fabricate a conformal separator around an electrode structure in a single pass.
- the conformal separator reduces shorting in a battery cell, ensuring safer batteries.
- the embodiments here remove the need to cut separator sheets larger than an electrode as a separator process.
- the electrode-separator structure can be reduced to a desired width, reducing the need for a slitting operation used in conventional battery manufacturing.
Description
- This disclosure relates to fabricating batteries, more particularly fabricating batteries using a co-extrusion apparatus.
- The use of a co-extrusion apparatus to manufacture various structures has been discussed in several patent applications and issued patents. A co-extrusion apparatus is one in which two or more materials are extruded simultaneously into a structure of some kind. This type of apparatus can be used in fabrication of batteries, simultaneously extruding electrodes with separators to form components of batteries.
- Examples of the co-extrusion approaches include
US Patent Publication 20120156364 , in which interdigitated fingers of co-extruded materials are extruded from one print head type of apparatus. The materials are fed into feeding channels and combined as separate flows, then split and combined again until a structure of alternating stripes of the two materials is created as they exit the print head. In another approach, the side-by-side lateral structure extends to interdigitated stripes in the vertical direction as well.US Patent Publication 20140186519 teaches a means to generate this type of structure. - The use of these structures to fabricate batteries is discussed in other publications, such as
US Patent No. 5,714,278 , in which a masked portion of the area of a porous separator material used in a battery. Masked areas can be formed on the porous separator material and allows for easier alignment of the anode and cathode sections to avoid edge effects. However, these areas are not formed in co-extrusion print heads. -
US Patent Publication No. 20110217585 discusses batteries having integrated separators and methods of fabricating such batteries. The separators are formed in different ways, but generally formed directly on either the cathode or anode. The separators may be single layer or multi-layered. These approaches do not form the electrodes and separators simultaneously in an extrusion manner. - Another approach uses electrophoretic deposition in sequential layers to form thin-film batteries. The sequential layers are formed using electrophoretic deposition. An example of this approach is shown in
US Patent Publication 20130244102 . - None of these approaches form the electrodes and separators simultaneously using a co-extrusion print head. These types of print heads have several advantages in their simplicity, their simultaneous deposition capability, but none exist that can form separator structures simultaneously with the electrodes. Because they are not formed simultaneously, the separator cannot be formed to be truly conformal to the electrode. Having a conformal separator provides a layer around the electrode to prevent the battery from shorting.
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US 2013/0133201 A1 describes a method for generating a microchannel heat pipe on a substrate by co-extruding a primary material and a secondary material.US 2014/0186519 A1 describes a co-extrusion print head for multi-layer battery structures that is capable of extruding at least two layers vertically in a single pass.US2007/0108229 A1 describes extruding composite materials on a substrate by feeding a first material into a first channel and a second material into one or more second channels residing on at least one side of the first channel. - The present invention provides, according to
claim 1, a co-extrusion print head that has at least one separator inlet port, at least a first, second and third series of channels arranged to receive a separator material from the separator inlet port, at least one electrode inlet port, a fourth series of channels arranged to receive an electrode material from the electrode inlet port, a first merge portion connected to the first, second, third and fourth series of channels, the first merge portion positioned to receive and merge all the separator material into separator flow and the electrode material into an electrode flow, a second merge portion connected to the first merge portion, the second merge portion positioned to receive and merge the separator flows and the electrode flows, and an outlet port comprising a first set of nozzles and a second set of nozzles, where the outlet port is connected to the second merge portion, wherein the outlet port is configured to distribute the separator material into the first set of nozzles and the electrode material into the second set of nozzles, wherein the first set of nozzles are arranged to the top of and to the sides of the second set of nozzles, where the first set of nozzles has at least one nozzle that is arranged to a first side of the second set of nozzles and at least one nozzle that is arranged to a second side of the second set of nozzles, wherein the at least one nozzle in the first set of nozzles that is arranged to the first side of the second set of nozzles and the at least one nozzle in the first set of nozzles that is arranged to the second side of the second set of nozzles are larger than the other nozzles in the first set of nozzles, and wherein the outlet port is configured to deposit a first portion of the separator material on top of the electrode material as a stack on a substrate and other portions of the separator material to the sides of the electrode material. - The dependent claims describe preferred embodiments.
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Figure 1 shows a prior art embodiment of a battery. -
Figure 2 shows a prior art embodiment of a process flow for manufacture of a battery. -
Figure 3 shows a prior art embodiment of a process flow for manufacture of a battery. -
Figures 4-7 show embodiments of a battery electrode having a conformal separator. -
Figure 8 shows an embodiment of a print head capable of forming stacked materials in one pass. -
Figure 9 shows an embodiment of a battery electrode having a conformal separator. -
Figures 10-15 show views of one embodiment of a print head capable of forming stacked layers on a substrate in one pass. -
Figures 16-18 show a process of formation of a conformal separator. -
Figures 19-22 show embodiments of a battery having a conformal separator. -
Figures 23-24 show an embodiment of a print head having a separator formed of multiple layers. - In a typical battery, the separator's primary function prevents physical contact between the anode and cathode while facilitating ion transport. This discussion will refer to the anode and cathode as electrodes.
Figure 1 shows a prior art embodiment of abattery 10 withcathode 16,anode 12 andseparator 14. During cell assembly, the separator has a larger area than that of either electrode. The process cuts the separator into a larger size than the anode and cathode electrodes. When inserted into a full cell assembly, the larger separator prevents edge/side contact between the electrodes. -
Figure 2 shows an example of a conventional battery manufacturing process for creating a full cell consisting of an anode, a cathode and a separator. As one can see, the process manufactures the anode in one clean. The process produces an anode slurry formation at 21, then slot coats it onto a current collector at 23, with calendaring for thickness control at 25. The process then dries the anode at 27. Similarly, the process forms a cathode slurry at 20, then slot coats it onto the current collector at 22 with calendaring for thickness control at 24. The cathode is dried at 26. Both electrodes undergo slitting at 29 and 28. Electrode slitting typically involves slitting a roll of electrode materials to a desired width. The final cell is then assembled at 31. - In the embodiments here, (
figure 3 ) theprocess 30 forms the anode, cathode and separator slurries at 32. The three slurries are then co-extruded using the print head disclosed here at 34 onto a current collector with calendaring for thickness control at 36. The combination of the structures are dried at 38. The remaining current collector is then assembled with the extruded structure at 40. -
Figures 4-7 show embodiments of battery structures manufacturable with the co-extrusion print head described here. InFigure 4 theelectrode 52 has a conformal separator that covers the top and sides of the electrode. Conformal, as that term is used here, means that the separator molds itself to the electrode. The electrode 42 may consist of a single material as inelectrode 52. Alternatively, the electrode may consist of an interdigitatedstructure 56 shown inFigure 5 . The interdigitated structure may result from the co-extrusion print head as discussed in the previous patents mentioned above. - In
Figures 6 and 7 , the separator conforms to the electrodes, but in addition to only covering the top and sides of the electrode, it also extends onto the current collector. This provides additional separation between the anode and cathode. InFigure 6 , theseparator 50 conforms to theelectrode 52 with extensions such as 54.Figure 7 shows the similar structure, but the electrode consists of an interdigitatedelectrode 56. - After the manufacture of these structures, they mate with the remaining electrode to form a full cell which is then cut or wound into the appropriate format. One can see that the co-extrusion enables a conformal separator to be fabricated around an electrode, while current manufacturing processes use a separator sheet cut to size in an area larger than the electrodes, leaving room for potential shorting at the sides during final cell assembly.
-
Figure 8 shows an embodiment of aprint head 62. Theprint head 62 extrudes the structures as viscous slurries onto atarget substrate 60. The materials may require drying or firing to remove the solvent and densify the structures. As shown inFigure 8 , theinlet ports electrode 52, or interdigitatedelectrode 56, andseparator 50, with or without theextension 54. - The print head of
Figure 8 , or a similar structure, can form the structures ofFigures 4-7 . Fluid paths and manifolds in the print head distribute separator and electrode slurries or inks. One can break down the structure ofFigure 6 into zones, as shown inFigure 9 . Theelectrode material 52 exits from one set of nozzles in the print head, as will be discussed inFigures 10-12 . The separator may consist of three different zones. Theextension 54 may consist of one slurry, referred to here as S1. Thesides 70 may consist of another slurry, referred to here as S2. Thetop layer 50 may consist of another slurry, S3. These slurries may all feed from the same slurry, forming a uniform layer over the electrode. Alternatively, the slurries may be different materials, to enable better isolation or enhance other characteristics of the batteries. The flows and feeds can be controlled as will be discussed in more detail later. -
Figure 10 shows a side view of one embodiment of aprint head 62. The print head has atop plate 82 that seals the print head and a back fixture plate for aligningparts 72. The ink enters through theback plate 72 and feeds into the nozzles throughmanifolds nozzle plates 78 form the extrusion nozzles through which the slurries ultimately exit the print head. -
Figure 11 shows a closer view of aportion 84 from theextrusion nozzles 78 fromFigure 10 . Theportion 86 is show in more detail inFigure 13 . The orientation of the print head is important to understand the configuration of the resulting structure. The substrate, which may consist of the current collector, is on the 'top' of the print head and the materials exit the print head with the electrode material E exiting the nozzles such as 94 being on the substrate first, then covered by the separator slurry S3 fromnozzle 96, with the separator slurry S2 from nozzles such as 92. The separator slurry S1 exits the print head at nozzles such as 90 and comes out onto the substrate in the same position as the electrode material. Walls such as 98 in the print head keep the materials isolated as they exit the interdigitation portion of the print head into a merge portion. -
Figure 13 shows the individual slurries separated from each other, the separator slurries and the electrode slurries are separated amongst themselves and from each other. The discussion ofFigures 13-15 may be better understood with reference toFigure 12 . InFigure 12 , theprint head 62 is shown in a block diagram. The print head has the inlet ports such as 64 for the separator slurry and 68 for the electrode slurry. The first portion of the print head hassections first merge portion 85 then allows the separator slurries to merge into a separator flow and aseparate portion 87 of the first merge portion to allow the electrodes to merge into an electrode flow. Asecond merge portion 89 then allows the separator flows and the electrode flows to merge together into one flow prior to exiting the print head at theoutput 91. These are shown inFigures 14 and15 are from the perspective of looking back from the outlet towards the nozzles from which the slurries flow. - In
Figure 14 , the slurries have traversed a first merge portion so the all of the separator 'S' slurries are merged together and all the 'E' slurries are merged together, but the 'S' slurries and 'E' slurries are still separate from each other. InFigure 15 , the 'S' slurries and 'E" slurries have merged. Note that this all occurs within the print head, and the resulting set of slurries exit the print head as merged flows, and the merged flows are in contact with each other but do not mix. -
Figures 16-18 illustrate a method of operation in which a layer of separator material that is wider than the electrode material. In these figures, the materials are being extruded in a direction either going into or out of the page. Theseparator material 50 is distributed into nozzles on top of and to the sides of the electrode material, forming a 'wider' stripe than the electrode material. This may be accomplished, in embodiments outside the scope of the present invention, without using the larger nozzles such as 92 shown inFigure 13 . - Just before the materials exit the print head, the
separator material 50 is 'higher' than the electrode material relative to thesubstrate 60. As the materials exit the print head, theseparator material 50 begins to flow overelectrode material 52 because it is no longer supported in the print head. Upon coming to rest on thesubstrate 60, theseparator 50 settles over the electrode material and forms theextensions 54. The portion of theseparator 50 that forms theextensions 54 will depend upon how many nozzles are used for the separator beyond the nozzles used for the electrode materials. -
Figures 19-22 show alternative embodiments of the battery structures having another layer on top of the top layer of separator S3. Typically, this layer will be a second top layer of separator, but may also consist of electrode material of the type opposite the first electrode. InFigure 19 , theelectrode 52 has theseparator 50 formed on top of it. In this embodiment, theopposite electrode 100 is formed on top of theseparator 50.Figure 20 shows the embodiment similar toFigure 19 , but with theinterdigitated electrodes 56.Figures 21 and 22 show the embodiments with an anode added to the separator that hasextensions 54 with and without the interdigitated electrodes. -
Figure 23 shows an alternative embodiment of a print head. In this embodiment, the stack ofplates 78 includes an extra set of extrusion nozzles. An exploded view of theportion 102 of theplates 78 is shown inFigure 24 . In this embodiment, thechannels 104 that dispense the separator S2 on the substrate next to the electrode material are larger than the previous S2 channels. Thenozzles 96 through which the slurry S3 exits the print head now have another set of nozzles adjacent them, such as 106. In this particular embodiment, the channels such as 106 dispense a fourth slurry S4 enables a multilayer composite separator. - In one embodiment, S3 and S4 consist of different separator materials. After drying, the S3 and S4 materials would have different materials, such a different porosity, insulating or thermal properties, etc. As previously mentioned, it is also possible that the additional slurry may be an electrode material that is of an opposite type of the first-used electrode material E. For example, if E is an anode material, S4 would be cathode material, or the opposite.
- In this manner, co-extrusion print heads can fabricate a conformal separator around an electrode structure in a single pass. The conformal separator reduces shorting in a battery cell, ensuring safer batteries. The embodiments here remove the need to cut separator sheets larger than an electrode as a separator process. The electrode-separator structure can be reduced to a desired width, reducing the need for a slitting operation used in conventional battery manufacturing.
- It will be appreciated that variants of the above-disclosed and other features and functions, or alternatives thereof, may be combined into many other different systems or applications. The scope of the invention is defined by the claims.
Claims (7)
- A co-extrusion print head (62), comprising:at least one separator inlet port (64);at least a first, second and third series of channels arranged to receive a separator material (50) from the separator inlet port (64);at least one electrode inlet port (68);a fourth series of channels arranged to receive an electrode material (52) from the electrode inlet port (68);a first merge portion (85) connected to the first, second, third and fourth series of channels, the first merge portion (85) positioned to receive and merge all the separator material (50) into a separator flow and all the electrode material (52) into an electrode flow;a second merge portion (89) connected to the first merge portion (85), the second merge portion (89) positioned to receive and merge the separator flows and the electrode flows; andan outlet port (91) comprising a first set of nozzles (90, 92, 96) and a second set of nozzles (94), where the outlet port is connected to the second merge portion (89), wherein the outlet port (91) is configured to distribute the separator material (50) into the first set of nozzles (90, 92, 96) and the electrode material (52) into the second set of nozzles (94), where the first set of nozzles (90, 92, 96) are arranged to the top of and to the sides of the second set of nozzles (94), where the first set of nozzles (90, 92, 96) has at least one nozzle (92) that is arranged to a first side of the second set of nozzles (94) and at least one nozzle that is arranged to a second side of the second set of nozzles (94), wherein the at least one nozzle in the first set of nozzles that is arranged to the first side of the second set of nozzles and the at least one nozzle in the first set of nozzles that is arranged to the second side of the second set of nozzles are larger than other nozzles (90, 96) in the first set of nozzles (90, 92, 96), and wherein the outlet port (91) is configured to deposit a first portion of the separator material (50) on top of the electrode material (52) as a stack on a substrate (60) and other portions of the separator material (50) to the sides of the electrode material (52).
- The co-extrusion print head (62) of claim 1, wherein the at least one separator inlet port (64) comprises three separator inlet ports.
- The co-extrusion print head (62) of claim 1, wherein the at least one electrode inlet port (68) comprises two electrode inlet ports.
- The co-extrusion print head (62) of claim 3, wherein the fourth series of channels are further arranged to receive two electrode materials.
- The co-extrusion print head (62) of claim 4, wherein the first merge portion (85) is arranged to receive the two electrode materials.
- The co-extrusion print head (62) of claim 5, wherein the outlet port (91) is arranged to deposit the two electrode materials as interdigitated stripes covered by the separator material (50) as the materials exit the print head (62).
- The co-extrusion print head (62) of claim 1, further comprising a fifth series of channels arranged to receive an additional material, the fifth series of channels connected to the second merge portion (89), and the outlet port (91) arranged to deposit the additional material on top of the separator material (50).
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US14/751,826 US9755221B2 (en) | 2015-06-26 | 2015-06-26 | Co-extruded conformal battery separator and electrode |
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EP3109028B1 true EP3109028B1 (en) | 2018-12-19 |
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EP16174205.1A Active EP3109028B1 (en) | 2015-06-26 | 2016-06-13 | Print head for co-extruding conformal battery separator and electrode |
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EP (1) | EP3109028B1 (en) |
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US11909083B2 (en) | 2018-12-28 | 2024-02-20 | Xerox Corporation | Apparatus and method for forming a multilayer extrusion comprising component layers of an electrochemical cell |
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US20160380254A1 (en) | 2016-12-29 |
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